Plural stage extractive distillation with inverse solvents



Jan. 13, 1948. R. c. MORRIS ETAL 2,434,424

PLURAL STAGE EXTRACTIVE DISTILLATION WITH DIVERSE SOLVENTS Filed March 1O, 19%? 2 Sheets-Sheet 1 FSOIWMX [L1 PFMWHQ mm WY Column biflfiltafioncolum J L Framer Extrad'ivc [4o Disflllahon Column Fig. l

lnvznl'orsz Ruperi' C. Morris Theodore Vt Eva-n bgmmm-m; qmm

Jan. 13, 1948. R. c. MORRIS ETAL 4.

PLURAL STAGE EXTRACTIVE DISTILLATIUN WITH INVERSB SOLVENTS Filed March 10, 1942 2 Sheets-Sheet 2 Toiucng Naz g 9 Q lnvzrriers'. Rupert C. Morris 8 r% Theodore W. Evans & g 3 a, me- Aflorm UNITED STATES PATENT OFFICE PLURAL STAGE EXTRACTIVE DISTILLATION WITH DIVERSE SOLVENTS Rupert 0. Morrls, Berkeley, and Theodore W.

Evans, Oakland, Calif asalgnorl to Shell Development Company, San Francisco, Call. a

corporation of Delaware Application March 10, 1942, Serial No. 434,115 9 Claims. (CL 202-395) The present invention relates to a process for separating distiilable mixtures. More particularly, it relates to a process for separating mixtures having such similar vapor pressures, or possessing such a tendency to form azeotropes with one another, as to make their separation difficult or impossible by ordinary distillation. Still more particularly, it relates to a process for the separation oi mixtures containing components which have different degrees 01' solubility in different solvents, e. g. hydrocarbon mixtures containing components of different degrees of saturation, etc.

It has long been recognized that it is impossible as a practical matter to separate by ordinary distillation certain mixtures containing components of very similar vapor pressures, or components which tend to form azeotropes with one another upon distillation. Examples of such mixtures are aromatic hydrocarbons such as benzene, toluene, the exylenes, etc., associated with paraflinic, naphthenic and olefinic hydrocarbons: synthetic mixtures of aromatics and non-aromatics, such as cyclohexane and benzene. alcohols and water, ethyl alcohol and water, ethyl alcohol and benzene. Many other mixtures of this type are known.

Several processes have been proposed to enable such mixtures to be separated; for example, it is sometimes possible to separate closely boiling mixtures by the addition of an azeotroplc agent.

It has also been proposed to separate components of similar boiling temperatures but difierent solubilities with the aid of a relatively high boiling solvent by distilling the mxiture in the presence of the liquid solvent. Under these conditions the relative vapor pressure of the more soluble component is reduced by a greater amount than the vapor pressure of the less soluble component, and in this manner it is sometimes possible to take overhead the less soluble component and subsequently separate the more soluble component from the relatively high boiling solvent in a separate distilling operation. This type of distillation has been termed extractive distillation, and it is wtih an improved method of extractive distillation that the present invention is particularly concerned.

Unfortunately, by extractive distillation it has not always been possible to effect satisfactory separations owing to slight differences in solubilities or because of the boiling ranges of the mixtures being too wide, etc. In such instances, in order to produce pure products by employing extractive distillation it is sometimes necessary to very carefully prei'ractionate the feed to be extractively distilled: for example, it has hereto- !ore been impossible to prepare nitration grade toluene from petroleum fractions by extractive distillation unless the feed to the extractive distillation system was very carefully prefractionated to exclude materials boiling more than about 10 C. above the boiling point of the toluene.

It is an object of the present invention to provide a process capable of producing pure components from mixtures which are normally dimcult to separate for the reasons given above. It is a further object to provide an improved process which permits pure components to be produced from hydrocarbon fractions not requiring careful preiractionation. A further ob- Ject is the production of a series of pure components from a relatively wide boiling range fraction containing a plurality of components of various types. Still further objects of our invention will be apparent from the following,

The present invention comprises distilling a mixture containing components having different solubilities in a first solvent under conditions to produce an overhead fraction comprising predominantly the least soluble component and a residual traction comprising the more soluble component, and subsequently distilling one or both of the fractions so produced in the presence of a different solvent which bears an inverse solubility relationship to the components as compared to the first solvent.

The invention may be more fully understood by consideration of the attached drawings, Figure I and Figure 11 being flow diagrams each representing different embodiments of the invention. Thus, Figure I is a flow diagram wherein a mixture comprising two components A and B (each of which components may comprise other components) are separated.

A feed mixture, which may be liquid or vaporous or both, comprising components A and B which normally are diificult to separate by ordinary distillation owing to similar vapor pressures, is fed through line I to primary extractive distillation column 2 provided with reboiler 3. The liquid in the bottom of the column is caused to boil by heat supplied by reboiler 3 so that vapors pass up through the column, which latter may be a packed, spray or bubble tray typ and thus flow countercurrently to a first relatively high boiling solvent X which is admitted to column 2 via line 4. Solvent X is of such nature that component A is more soluble therein than component B, and therefore the relative vapor pressure of A is decreased with respect to that of B.

Owing to difllculties inherent in such operations it is normally impracticable to cut sharply between component A on the one hand and component B on the other. Thus, it is ordinarily impossible to take overhead pure B without leaving a small residual quantity or B in the solvent along with A; or conversely, if the solvent is to contain pure A and be substantially free from B. it is practically impossible to prevent a small quantity of A from passing overhead with B. If it is desired to produce both A and B in pure form, additional steps must be taken, and these subsequent steps depend upon whether in column 2 B is being taken overhead substantially free from A, or a solution of pure A substantially free from B in the solvent is withdrawn from the bottom of the column 2.

In the first case, vapors of pure B substantially free from solvent and A pass overhead through line 5 to condenser 0. Liquefied component B collects in accumulator I whence a portion is returned to column 2 via line as reflux, while the remaining portion is withdrawn via valved line 9 (valve l0 being closed) as final product. Fat solvent X containing dissolved A and a minor portion of B is withdrawn from column 2 via line H, passing to primary stripping column i2 provided with reboiler l3. Herein solvent X is separated from components A and B and returned back to column 2 via line H, cooler I5 and line 4 for use in another cycle.

Vapors of A and B pass overhead through line It to condenser l1. Condensate collects in accumulator l8 whence a portion is returned to column |2 as reflux via line l0. The remaining portion of A+B passes via valved line 20 to secondary extractive distillation column 2| provided with reboiler 22.

Herein the feed is distilled in the presence of a second solvent Y admitted via line 33. Solvent Y bears the inverse solubility relationship with respect to components A and B to solvent X; that is, Y has greater solvent power for B than for A. Under these circumstances, by careful control of heat input, reflux ratio and solvent feed rate. A substantially free of B is taken overhead through line 23 to condenser 24. Condensed vapors collect in accumulator 25, whence a portion i returned to column 2| as reflux via line 20. while the remaining portion may be withdrawn through line 21 as final product. Solvent Y containing dissolved B and a minor portion of A is withdrawn from the bottom of column 2| through line". passing to secondary stripping column 29 provided with reboiler 00. Herein solvent Y is separated from residual A and B, the former returning to column 2| via line 0|, cooler 22 and line 38, for use in another cycle. Residual quantitles or A and B pass overhead through'line 34 to condenser 35. Condensed vapor collect in accumulator 38 whence a portion may be returned to column 20 via line 31 as reflux. The remaining portion of residual A+B may be discarded via valved line 38 (valve 00 being closed) or else may be returned to a level in column 2 where the vapor composition is the same or near to the composition or the recycled material via line 40 and the manifold system comprising valves 42, 43, 44, 45 and bypass line 40, to recover residual quantities of A-i-B (valve 80 being closed).

In the second variation. vapors of B containing a minor portion of A pass overhead through line i to condenser I. Liquefied components A and B collect in accumulator I whence a portion is returned to column 2 via line 0 as reflux, while the remaining portion passes via valved line I 0 (valve 0 being closed) and line 20 to column 2|.

From the bottom of column 2 solvent containing substantially pure A is withdrawn via line H. passing to column l2. I -Ierein the solvent is separated from dissolved component A, the former being returned to column 2 via line l4, cooler ii and line 4, for use in another cycle. Overhead vapors consisting of substantially pure A pass via line ii to condenser l. Condensed A collects in accumulator I8. whence a portion is returned as reflux to column l2 via line i9, while the remainder is withdrawn as final product via valved line 4| (valve 20 being closed).

The mixture A+B from line |0 being fed to column 2| is treated similarly to A-i-B described above, except that, it it is desired to produce both components A and B in pure form, column 2| should be operated under conditions to take a portion of B overhead with the A in order to re move solvent and B from the bottom of column 2| free from A. Pure B is then withdrawn from the system via line 30 (valve 30 being closed). Under these circumstances the produce withdrawn from line 21 is a mixture of A+B and may be discarded or recycled to the feed for further treatment in a manner similar to that of the product described above withdrawn through valved line 00.

If it is desired to produce only A in pure form, then column 2| may be operated to take overhead A substantially free from B, and pure prodnot A is withdrawn via line 21 as well as from valved line 40, while a mixture of A+B is withdrawn via line 38. In such a case the relative proportions of A+B are diflerent, which may require diilerent solvent-to-feed rates from those required in the first operation. It will be understood that in certain cases it may be desirable to first employ solvent Y in column 2 followed by treatment with solvent X in column 2|. The exact manner in which the separation is carried out will depend upon the particular separation under consideration, the relative proportions of components in the feed to the various columns, and the desired degree of separation to be obtained.

Figure II illustrates another embodiment of the present invention wherein a series oi pure aromatic hydrocarbon fractions are produced from a mixture containing other hydrocarbons which tend to form azeotropes with aromatic hydrocarbons.

A feed, such as a straight-run gasoline fraction boiling between 63 C. and 147 0., containing small percentages 01 benzene, toluene, ortho-, metaand para-xylenes and ethyl benzene, and paraiiinic and naphthenic hydrocarbons naturally associated therewith (hereinafter designated as non-aromatic hydrocarbons) is fed continuously via line |0| to fractionatlng column I02 equipped with reboiler I03. Herein the feed is contacted with a relatively high-boiling polar selective solvent for aromatic hydrocarbons such as a narrow-boiling alkyl phenol mixture, for example one boiling between 210 C. and 220 C. (hereinafter referred to as polar solvent), which is admitted through line I04 and passes down the column as the distillation proceeds. The presence of the solvent reduces the relative vapor pressure of the aromatic hydrocarbons more than that of the non-aromatic hydrocarbons, and by controlling the reflux ratio and solvent ratio, column I02 is so regulated that almost all of the non-aromatic hydrocarbons which do pass overhead through line I05, normally in the absence of selective solvent would form azeotropes with benzene; while the benzene and higher boiling aromatics together with the relatively high boiling non-aromatic hydrocarbons pass from the bottom of column I02. The overhead vapors are condensed in condenser I05 and collected in accumulator I01. A portion of this condensate is returned to column I02 as reflux through line I08, the remainder passin to storage not shown through line I09.

From the bottom of column I02 the residue, including benzene and only minor quantities of non-aromatics which normally tend to form azeotropes with benzene, pass through line IIO to i'rwctionating column II I equipped with reboiler I I2. Herein the hydrocarbons are separated from the polar solvent, which is withdrawn from the bottom of column II I through line I04 substantially free from hydrocarbons, and is recycled to column I02. If desired, the recovered solvent may be first cooled before returning to column I02 in coolers (not shown) or be admitted hot. The overhead hydrocarbon vapors pass through line II3 to condenser II4. Condensed vapors collect in accumulator II5, whence a portion of the condensate is returned to column III as reflux via line IIB. while the remainder passes via line II1 to iractionating column II B equipped with reboiler I I9.

In column lIIl the hydrocarbon mixture is contacted with a relatively high boiling non-polar solvent, such as paraflin wax, admitted via line I20. The paraifln wax, although not so selective for non-aromatic hydrocarbons as polar solvents are, in general. for aromatic hydrocarbons, nonetheless suiflce to reduce the relative vapor pressure of the small residual quantities of non-aromatic hydrocarbons that would otherwise form azeotropes with benzene to a degree which, in conjunction with careful control of reflux and solvent ratios to column II8, allows pure benzene vapors to be taken overhead through line I2I to condenser I22. Liquid benzene collects in accumulator I23, whence a portion is returned to column II8 as reflux through line I24, while the remainder passes to storage not shown as a pure benzene product through line I25.

Residual gasoline hydrocarbons dissolved in the non-polar solvent pass through line I28 to i'ractionating column I21 equipped with reboiler I28. Therein the mixture is fractionally distilled into solvent substantially free from gasoline hydrocarbons, which solvent is recirculated to column I I8 through line I20, and an overhead vapor comprising the gasoline hydrocarbons, which passes overhead through line I23 to condenser I30. Condensate collects in accumulator I3I, a portion of which is returned to column I21 "la line I32 as reflux, while the remainder passes through line I33 to column I34 equipped with reboiler I35. In column I34 the feed is contacted with another portion of polar solvent, which is admitted through line I36 and serves to reduce the relative vapor pressure of the aromatic hydrocarbons including toluene so that by careful control of the reflux and solvent ratios, etc., it is possible to take overhead as vapors most of the non-aromatic hydrocarbons which normally, in the absence of solvent, would pass overhead with the toluene as azeotropes, as well as the small amounts of the non-aromatic hydrocarbons which would have formed azeotropes with the benzene in the ab sence of the non-polar solvent in column I02 but which instead were carried away as bottom product from column I02 together with the polar solvent through line IIO. These vapors pass overhead through line I31 to condenser I30. Condensate collects in accumulator I29, whence a portion passes back to column I34 as reflux via line I40 while the remainder passes to storage not shown, through line I4 I.

The residual hydrocarbons from column I34, including toluene and only very minor quantities of hydrocarbons which normally tend to form azeotropes with toluene, together with heavier hydrocarbons and polar solvent, pass through line I42 to column I43 equipped with reboiler I44. Herein the solution is fractionally distilled, solvent being recycled to column I34 through line I30, while the vaporized hydrocarbons pass overhead through line I45 to condenser I48. Condensed hydrocarbons collect in accumulator I41. A portion of the condensate is returned to column I43 as reflux via line I48 while the remaining portion passes via line I49 to column I50 equipped with reboiler I5I.

Herein the hydrocarbon feed is contacted with non-polar solvent admitted through lines I52. The latter lowers the relative vapor pressure of small residual quantities or non-aromatic hydrocarbons which, in the absence or solvent, would pass overhead as azeotrope with toluene, thus permitting vapors of nitration grade toluene to pass overhead through line I53 to condenser I54. Cordensed toluene collects in accumulator I55. A portion of the toluene is returned to column I50 as reflux via line I56 while the remainder passes via line I 51 to storage (not shown).

The residual hydrocarbons now free from toluene but still containing xylenes and ethyl benzene, non-aromatic hydrocarbons normally associated therewith, as well as the small residual quantities of non-aromatics which would normally pass overhead with toluene, pass via line I58 to column I58 equipped with reboiler I00, wherein they are separated from non-polar solvent by fractional distillation, solvent recirculating back to column I50 via line I52. The mixed hydrocarbon vapors pass overhead via line I6I to condenser I52. Condensate collects In accumulator I53 whence a portion returns via line I64 as reflux while the remainder passes via line I65 to column I08 equipped with reboiler I61.

The feed to column I66, which by now is only a small portion of the original fraction distilled, is again contacted with polar solvent admitted via line I58, which reduces the relative vapor pressure of remaining aromatic hydrocarbons, that is the xylenes and ethyl benzene, permitting practically all of the non-aromatic hydrocarbons which would normally form azeotropes with the xylenes and ethyl benzene to pass overhead along with small residual quantities of non-aromatic hydrocarbons that were prevented from passing overhead as azeotrope with the toluene in column I50. The mixed hydrocarbon vapors pass through line I69 to condenser I10. Condensate collects in accumulator I1I, whence a portion is returned via line I12 to column IE6 as reflux while the remainder passes to storage (not shown) through line I13.

From the bottom of column I66 a mixture comprising predominantly xylenes, ethyl benzene and polar solvent is withdrawn through line I14 and passes to column I15 equipped with reboiler I16. Herein the polar solvent is separated from the xylenes and ethyl benzene, recirculating back to column I55 through line I 60 for use in another cycle, while the vapors pass overhead via line lll to condense: H8. Condensate collects in accumulator I19, whence a portion returns to column H as reflux via. line I80, while the remainder passes via line i8l to storage not shown.

Although the xylenes so produced contain small residual portions of nomaromatic hydrocarbons, they may often be employed for commercial purposes in this state. However, if desired, they can be further freed from non-aromatic hydrocarbons by subjecting the product from line 1 8| to further stages of treatment, as described before, with alternate solvents.

Although in the foregoing description the same non-polar and polar solvents have been indicated in each corresponding stage, this is not necessary because, if desired, diilerent polar solvents may be employed in the "polar" stages and, likewise. different non-polar solvents may be employed in the various "non-polar" stages without departing from the spirit of the present invention.

In the treatment of hydrocarbon mixtures, for example petroleum distlllates, it is generally preferable to employ the polar solvent first, followed by treatment with the non-polar solvent. In this manner the normal tendency for any light hydrocarbon ends to come overhead in enhanced, resulting in initially reducing the amount of material to be treated with non-polar solvent in subsequent operations.

In this connection it may bepointed out that the present invention takes advantage, in the case of separations of hydrocarbons having difierent degrees of saturation, of the initial reduction of the quantity of more saturated hydrocarbons. By following this preferred sequence the residual hydrocarbon mixture separated from the first treatment with polar solvent contains only relatively small amounts of saturated hydrocarbons which tend to form azeotropes with the less saturated hydrocarbons, because polar solvents are available which have very high selectivity for the more unsaturated compounds. As a result, the remaining saturated hydrocarbons can be effectively prevented from going overhead in the subsequent distillation in the presence of nonpolar solvent, even though in general the selectivity of the known non-polar solvents for more saturated hydrocarbons is relatively poor.

For simplicity, bypasses. pumps, heat exchangers, valves, control means and other auxiliaries, the proper placement of which is evident to one skilled in the art, have been omitted.

As can be seen from the foregoing, the present invention has wide applicability, being applicable to any ordinarily diflicult separation, depending upon differences in vapor pressure, for which there exists a pair of "inverse" solvents. In other words, the present process is applicable to the separation of any two components A and B (which themselves may be multi-component mixtures) having such similar vapor pressures as to make their separation by ordinary distillation difllcult, provided a pair of relatively high boiling solvents X and Y exist bearing the following relationship:

can be attained.

Examples of processes to which the present invention is particularly applicable are those in which so-called polar and non-polar solvents are employed alternately for the separation oi fatty oils. fatty acids, amines. alcohols, nitrogen bases, essential oils, mixed chlorinated hydrocarbons, phenol and thiophenol mixtures, naval store products, and hydrocarbon mixtures, particularly those containin hydrocarbons or different de grees of saturation. For example, aromatic hydrocarbons of high purity can be separated from non-aromatic hydrocarbons of diilerent degrees of saturation which occur in fractions derived from petroleum through distLlation, cracking, dehydrogenation, hydrogenation, isomerization, cyclization, hydroforming, etc. A single aromatic hydrocarbon such as toluene of nitration grade may be prepared by employing alternately a polar solvent such as phenol, and a non-polar solvent such as paraflln wax, or a paraflinic mineral oil having a "characterization factor" as defined by Watson et al., Ind. Eng. Chem., vol, 27 (1935), pp. 1460-1464, of at least 12.0, and having a boiling range sufllciently high to remain at least partially liquid during the extractive distillation.

Suitable non-polar solvents may be prepared from several sources, for example petroleum, synthetic hydrocarbon fractions which themselves may be derived from petroleum, or other hydrocarbon fractions, for example those prepared by the hydrogenation of coal or the Fischer-Tropsch synthesis (CO+Hz+catalyst) etc. Suitable starting materials are subjected to distillation, solvent extraction, extractive distillation, or chemical treatment, for example with strong sulfuric acid, or by a combination of these treatments to remove aromatic type hydrocarbons and produce a solvent of appropriate boiling range.

Examples of polar solvents which are useful for separations of this type are: phenol, cresylic acids, alkyl' phenol mixtures, aniline, aikyl anilines, diphenylamlnes, ditolylamines; carbitols (diethyiene glycol mono ethers) such as methyl, ethyl, propyl carbitols: chlorinated dialkyl ethers such as beta-beta-dichlorethyl ether; nitrobenzene, nitrotoluene, nltroxylenes; naphthols, alkyl naphthols, benzophenone, phenyl tolyl ketone, diphenylene ketone; alkyi phthalates, such as dimethyl phthalate; aikyl salicylates, such as methyl salicylate; benzyl alcohol, benz chlorides, i. e. benzyl, benzal, benzo chlorides; benzonitrile, diphenyl oxide, ditolyl oxide, hydroxy pyridine, nitropyridine, chlorinated pyridines, quinoline, isoquinoline, chlorinated quinoline, hydroxy quinolines, 5-nitro quinoline, tetra hydro furiuryl alcohol, turfuryl alcohol, furfurai, the mono glycerol ethers such as l-methoxy glycerol, 2-methoxy glycerol, l-ethoxy glycerol. 2-ethoxy glycerol, l-propoxy glycerol, z-propoxy glycerol, l-isopropoxy glycerol, 2-isopropoxy glycerol; the glycerol di-ethers, such as i,2-dimethoxy glycerol, 1,3-dimethoxy glycerol, 1,2-diethoxy glycerol, l,3-dlethoxy g ycerol, l,2-dipropoxy glycerol, 1,3-dipropoxy glycerol, 1,2-di-isopropoxy glycerol, and 1,3- di-isopropoxy glycerol; the mixed diglycerol ether esters, such as l-ethoxy, Z-methon gycerol, 1- methoxy, 3-propoxy glycerol, l-ethoxy, 2-isopropoxy glycerol; antimony trichlorlde; various sulfones, etc.

Our process is further applicable to the separation of isomeric substances with appropriate higher boiling polar and non-polar solvents such as are disclosed in U. S. Patent 2,245,945.

Likewise, the invention is applicable when it is desired to separate a series of hydrocarbons oi 9 diflerent degrees of saturation from a relatively wide boiling hydrocarbon fraction from petroleum and coal tar sources.

Butadiene in a. highly pure form may be separated from mixed C4 petroleum fractions by first distilling in the presence of a polar solvent to take a mixture of butadiene and beta-butylene oil the bottom with the solvent, which mixture is separated from the solvent and subsequently distilled in the presence of a non-polar solvent such as a relatively narrow boiling paraflinic kerosene fraction to take the butadiene overhead in a substantially pure condition and recover the beta-butylene as a bottom product.

Sometimes, however, when the relatively nonpolar component of greater natural volatility than that of the relatively more polar component is present in small quantities only, it is desirable to employ non-polar solvent first, followed by fractionation in the presence of a polar solvent. Such is the situation when separating a C4 fraction containing a major portion of beta-butylene and butadiene and a minor portion only of alphabutylene.

The foregoing examples included for purposes of illustration only will suggest many other applications to other distillation problems of the principle of inverse solvents as set forth in the present specification.

In the specification and claims, by ordinary distillation is meant any distillation in the absence of added selective solvents or azeotropeforming agents.

It will be further understood that components des gnated by the letters A, B, C. etc., may themselves be multi-component mixtures or pure chemical compounds, e. g. the letter A may represent a mixture of saturated hydrocarbons of close boilin range which are normally associated with and boil close to a single aromatic hydrocarbon such as toluene, which may itself be represented by the letter A.

We claim as our invention:

1. A process for separating butadiene from a C4 hydrocarbon mixture comprising butadiene, beta butylene and more saturated C4 hydrocarbons, comprising the steps of extractively distilling said mixture in the presence of a ,first relatively high boiling polar solvent under conditions to produce a first overhead fraction comprising said more saturated hydrocarbons and a residual fraction comprising butadiene, beta butylene and said solvent, separating said solvent from said residual fraction, and extractively distilling at least a part of said residual fraction in the presence of a relatively high boiling non-polar solvent for beta butylene under conditions to take butadiene overhead.

2. In a process for separating a mixture comprising a pair of relatively low boiling vaporizable components A and B and a pair of relatively high boiling vaporizable components C and D, the members of each of said pairs of components being not readily separable from each other by ordinary distillation, A being more soluble than B in a relatively high boiling solvent W, B being more soluble than A in a relatively high boiling solvent X, and C being more soluble than D in a relatively high boiling solvent Y, the steps of distilling said mixture in the presence of said solvent W under conditions to take overhead B and leave a residue comprising components A, C and D dissolved in solvent W, separating W from said residual components, distilling said residual components in the presence of solvent X under conditions to take overhead A and leave a second residue comprising components 0 and D dissolved in solvent X, separating said second residual components from solvent X, and distilling them in the presence of solvent Y under conditions to take overhead D and leave a third residue comprising C dissolved in solvent Y.

3. The process of claim 2 wherein said solvents W and Y are polar solvents, and solvent X is a non-polar solvent.

4. The process of claim 2 wherein W and Y are the same polar solvent.

5. In a process for separating a vaporizable hydrocarbon mixture comprising at least two aromatic hydrocarbons diilering from each other in carbon content by not more than one carbon atom, together with more saturated hydrocarbons having vapor pressures in the presence of said aromatic hydrocarbons so similar to the vapor pressures oi said aromatic hydrocarbons as to prevent said saturated hydrocarbons from being readily separated from said aromatic hydrocarbons by ordinary distillation, the steps of distilling said mixture in the presence of a relatively high boiling polar solvent under conditions to take overhead 8. first portion 01' said more saturated hydrocarbons normally having vapor pressures similar to the vapor pressure of the lower boiling of said aromatic hydrocarbons and leave a residue comprising said aromatic hydrocarbons and a second portion of said more saturated hydrocarbons, having vapor pressure similar to the vapor pressure of the higher boiling aromatic hydrocarbon, dissolved in said relatively high boiling polar solvent, separating said polar solvent from said residual components, distilling said residual components in the presence of a relatively high boiling non-polar solvent under conditions to take overhead said lower boiling aromatic hydrocarbon and leave a second residue comprising the relatively high boiling aromatic hydrocarbon and at least a part of said second portion of said more saturated hydrocarbons dissolved in said non-polar solvent, separating said dissolved bydrocarbons from said non-polar solvent and dist lling them in the presence of a relatively high boiling polar solvent under conditions to take overhead at least a part of said second portion of said more saturated hydrocarbons and to leave a third residue comprising said relatively high boiling aromatic hydrocarbon dissolved in said polar solvent.

6. In a process for separating a hydrocarbon mixture comprising benzene and toluene and more saturated hydrocarbons having in the presence of benzene and toluene vapor pressures so similar to the vapor pressures of benzene and toluene as to prevent said saturated hydrocarbons from being readily separated from said aromatic hydrocarbons by ordinary distillation, the steps of distilling said hydrocarbon mixture in the presence of a relatively high boiling polar solvent under conditions to take overhead a first portion of said more saturated hydrocarbons having vapor pressures similar to benzene and leave a residue comprising benzene, toluene and a second portion of said more saturated hydrocarbons, having vapor pressures similar to toluene, dissolved in said solvent, separating said solvent from said residual hydrocarbons, distilling said residual hydrocarbons in the presence of a relatively high boiling non-polar solvent under conditions to take overhead benzene and leave a second residue comprising toluene and at least a part of said second portion of said more saturated hydrocarbons dissolved in said non-polar solvent, separating said second residual hydrocarbons from said non-polar solvent, distilling said second residual hydrocarbons in the presence of a relatively high boiling polar solvent under conditions to take overhead at least a part at said second portion of more saturated hydrocarbons and leave a third residue comprising toluene dissolved in said polar solvent.

7. In a process for separating a vaporizable hydrocarbon mixture comprising at least two aromatie hydrocarbons diflering from each other in carbon content by not more than one carbon atom, together with more saturated hydrocarbons having vapor pressures in the presence or said aromatic hydrocarbons so similar to the vapor pressures oi said aromatic hydrocarbons as to prevent said saturated hydrocarbons irom being readily separated from said aromatic hydrocarbons by ordinary distillation, the steps of distilling said mixture in the presence of a relatively high boiling non-polar solvent under conditions to take overhead the lower boiling of said aromatic hydrocarbons and leave a residue comprising the higher boiling aromatic hydrocarbon and said more saturated hydrocarbons dissolved in said relatively high boiling non-polar solvent, separating said non-polar solvent from said residual components, distilling said residual components in the presence Of a relatively high boiling polar solvent under conditions to take overhead a first portion of said more saturated hydrocarbons having vapor pressures similar to the vapor pressure of the lower boiling aromatic hydrocarbon and leave a second residue comprising the relatively high boiling aromatic hydrocarbon and a second portion of the more saturated hydrocarbons, normally having vapor pressures sim ilar to the vapor pressure of said higher boiling aromatic hydrocarbon, dissolved in said polar solvent, separating said dissolved hydrocarbons from said polar solvent and distilling them in the presence of a relatively high boiling non-polar solvent under conditions to take overhead said relatively high boiling aromatic hydrocarbon and leave a third residue comprising at least a part 01' said second portion of said more saturated hydrocarbons dissolved in said non-polar solvent.

8. In a process for separating a vaporizable hydrocarbon mixture comprising toluene and Cs aromatic hydrocarbons and more saturated hydrocarbons having in the presence of said aromatic hydrocarbons vapor pressures so similar to the vapor pressures of said aromatic hydrocarbons as to prevent said saturated hydrocarbons from being readily separated from said aromatic hydrocarbons by ordinary distillation, the steps of distilling said hydrocarbon mixture in the presence or a relatively high boiling polar solvent under conditions to take overhead a first portion of said more saturated hydrocarbons having vapor pressures similar to toluene and leave a residue comprising Cs aromatic hydrocarbons and a second portion of said more saturated hydrocarbons, having vapor pressures similar to said Cs aromatic hydrocarbons, dissolved in said solvent. separating said solvent from said residual hydrocarbons, distilling said residual hydrocarbons in the presence oi a relatively high boiling non-polar solvent under conditions to take overhead toluene and leave a second residue comprising said Ca aromatic hydrocarbons and at least a part 01' said second portion of said more saturated hydrocarbons dissolved in said nonpolar solvent, distilling said second residual hydrocarbons in the presence or a relatively high boiling polar solvent under conditions to take overhead at least a part of said second portion oi more saturated hydrocarbons and to leave a residue comprising said Cs aromatic hydrocarbons dissolved in said polar solvent.

9. A process for separating a C4 hydrocarbon mixture comprising a major portion or butadlene and beta-butylene and a minor portion of alphabutylene, comprising the steps of extractively distilling said mixture in the presence of a first relatively high boiling non-polar solvent under con ditions to produce a first overhead traction rich in butadiene and alpha-butylene and a residual traction rich in beta-butylene and said solvent, further extractively distilling at least a part of said overhead fraction in the presence of a polar solvent under conditions to take overhead alphabutylene and leave a residual traction comprising said polar solvent and being rich in butadiene.

RUPERT o. Mortars. THEODORE w. EVANS.

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